WO2022045187A1 - Film optique, plaque de polarisation circulaire et dispositif d'affichage électroluminescent organique - Google Patents
Film optique, plaque de polarisation circulaire et dispositif d'affichage électroluminescent organique Download PDFInfo
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- WO2022045187A1 WO2022045187A1 PCT/JP2021/031144 JP2021031144W WO2022045187A1 WO 2022045187 A1 WO2022045187 A1 WO 2022045187A1 JP 2021031144 W JP2021031144 W JP 2021031144W WO 2022045187 A1 WO2022045187 A1 WO 2022045187A1
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- optically anisotropic
- anisotropic layer
- liquid crystal
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- crystal compound
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Images
Classifications
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3016—Polarising elements involving passive liquid crystal elements
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
- G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
- G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
- G02B5/305—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks including organic materials, e.g. polymeric layers
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/13363—Birefringent elements, e.g. for optical compensation
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
-
- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
- G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/02—Details
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/80—Constructional details
- H10K59/8791—Arrangements for improving contrast, e.g. preventing reflection of ambient light
Definitions
- the present invention relates to an optical film, a circular polarizing plate, and an organic electroluminescence display device.
- optically anisotropic layer having a refractive index anisotropy is applied to various applications such as an antireflection film for an organic electroluminescence (EL) display device and an optical compensation film for a liquid crystal display device.
- EL organic electroluminescence
- Patent Document 1 discloses a retardation plate in which two types of optically anisotropic layers exhibiting predetermined optical characteristics are laminated.
- the present inventors examined the optical film in which the optically anisotropic layers described in Patent Document 1 were laminated, and confirmed that there was room for improvement in the adhesion between the directly laminated optically anisotropic layers. did.
- adhesion between the directly laminated optically anisotropic layers is simply referred to as “adhesion”.
- An object of the present invention is to provide an optical film having excellent adhesion. Another object of the present invention is to provide a circularly polarizing plate and an organic EL display device.
- the optically anisotropic layer (C) is a layer formed by immobilizing a vertically oriented rod-shaped liquid crystal compound or a horizontally oriented disk-shaped liquid crystal compound containing a photo-oriented polymer having a photo-oriented group.
- optical film in which a photoalignable polymer is present on the surface of the optically anisotropic layer (C) on the side in contact with the optically anisotropic layer (A) or the optically anisotropic layer (B).
- the photo-oriented group is a photo-oriented group in which at least one of dimerization and isomerization is generated by the action of light.
- the photo-oriented group is a group selected from the group consisting of a cinnamoyle group, an azobenzene group, a carconyl group, and a coumarin group.
- the optically anisotropic layer (A) is an optically anisotropic layer formed by immobilizing a vertically oriented disk-shaped liquid crystal compound.
- the optically anisotropic layer (B) is an optically anisotropic layer formed by fixing a rod-shaped liquid crystal compound twist-oriented having a spiral axis in the thickness direction.
- the optically anisotropic layer (C) is an optically anisotropic layer formed by immobilizing a vertically oriented rod-shaped liquid crystal compound.
- the optically anisotropic layer (A), the optically anisotropic layer (B), and the optically anisotropic layer (C) are provided in this order, and the optically anisotropic layer (B) and the optically anisotropic layer (C) are provided in this order.
- the optical film according to any one of [1] to [4], which is directly laminated with and.
- the optically anisotropic layer (A) is an optically anisotropic layer formed by immobilizing a horizontally oriented rod-shaped liquid crystal compound.
- the optically anisotropic layer (B) is an optically anisotropic layer formed by fixing a rod-shaped liquid crystal compound twist-oriented having a spiral axis in the thickness direction.
- the optically anisotropic layer (C) is an optically anisotropic layer formed by immobilizing a vertically oriented rod-shaped liquid crystal compound.
- the optically anisotropic layer (A), the optically anisotropic layer (C), and the optically anisotropic layer (B) are provided in this order, and the optically anisotropic layer (A) and the optically anisotropic layer (C) are provided in this order.
- the optical film according to any one of [1] to [6] and a polarizing element are provided.
- a circular polarizing plate in which a splitter is arranged adjacent to an optically anisotropic layer (A) of an optical film.
- an optical film having excellent adhesion it is possible to provide an optical film having excellent adhesion. Further, according to the present invention, it is possible to provide a circularly polarizing plate and an organic EL display device.
- FIG. 1 is a schematic cross-sectional view showing an example of an embodiment of the optical film of the present invention.
- FIG. 2 is a schematic cross-sectional view showing an example of an embodiment of the optical film of the present invention.
- FIG. 3 is a schematic cross-sectional view showing an example of an embodiment of the circular polarizing plate of the present invention.
- FIG. 4 is a schematic cross-sectional view showing an example of an embodiment of the circular polarizing plate of the present invention.
- the numerical range represented by using "-" means a range including the numerical values before and after "-" as the lower limit value and the upper limit value.
- a substance corresponding to each component may be used alone or in combination of two or more.
- the content of the component means the total content of the substances used in combination unless otherwise specified.
- (meth) acrylic is a notation representing "acrylic” or "methacrylic”.
- the slow axis is defined at 550 nm unless otherwise specified.
- Re ( ⁇ ) and Rth ( ⁇ ) represent in-plane retardation at wavelength ⁇ and retardation in the thickness direction, respectively. Unless otherwise specified, the wavelength ⁇ is 550 nm.
- the values of the average refractive index of the main optical films are exemplified below: cellulose acylate (1.48), cycloolefin polymer (1.52), polycarbonate (1.59), polymethylmethacrylate (1.49), And polystyrene (1.59).
- the term "light” means active light or radiation, for example, the emission line spectrum of a mercury lamp, far ultraviolet rays typified by an excima laser, extreme ultraviolet rays (EUV light), X-rays, ultraviolet rays, and the like. And means electron beam (EB) and the like. Of these, ultraviolet rays are preferable.
- visible light refers to light having a diameter of 380 to 780 nm.
- the measurement wavelength is 550 nm.
- the relationship between angles includes a range of errors allowed in the technical field to which the present invention belongs. Specifically, it means that the angle is within a range of less than ⁇ 10 °, and the error from the exact angle is preferably within a range of ⁇ 5 ° or less, and within a range of ⁇ 3 ° or less. Is more preferable.
- the horizontal orientation of the rod-shaped liquid crystal compound means a state in which the long axis of the liquid crystal compound is arranged horizontally and in the same direction with respect to the layer surface.
- the term “horizontal” does not require that the liquid crystal compound be strictly horizontal, but means an orientation in which the inclination angle formed by the average molecular axis of the liquid crystal compound in the layer and the surface of the layer is less than 20 °.
- the same direction does not require that the directions are exactly the same, and when the directions of the slow phase axes are measured at arbitrary 20 positions in the plane, the slow phase axes at 20 points are measured.
- the maximum difference between the slow-phase axis directions among the two directions is less than 10 °. ..
- the vertical orientation of the disk-shaped liquid crystal compound means a state in which the disk axes of the liquid crystal compound are arranged perpendicularly to the layer surface and in the same direction.
- the term "perpendicular” does not require that the liquid crystal compound be strictly vertical, but means that the inclination angle formed by the disk surface of the liquid crystal compound in the layer and the surface of the layer is 70 to 110 °.
- the same direction does not require that the directions are exactly the same, and when the directions of the slow phase axes are measured at arbitrary 20 positions in the plane, the slow phase axes at 20 points are measured. It is assumed that the maximum difference between the slow-phase axis directions among the two directions (the difference between the two slow-phase axis directions having the maximum difference among the 20 slow-phase axis directions) is less than 10 °. ..
- the optically anisotropic layer may be a layer exhibiting predetermined optical characteristics, and is preferably a layer having a fixed alignment state of the oriented liquid crystal compound, for example.
- the "fixed" state is a state in which the orientation of the liquid crystal compound is maintained.
- the layer has no fluidity in the temperature range of 0 to 50 ° C., usually -30 to 70 ° C. under more severe conditions, and the orientation morphology is changed by an external field or an external force. It is more preferable that the state is such that the fixed orientation form can be kept stable.
- the optically anisotropic layer contained in the optical film of the present invention is preferably a layer formed by immobilizing a vertically oriented rod-shaped liquid crystal compound or a horizontally oriented disc-shaped liquid crystal compound. From the usefulness that it can be used as a compensating layer for a circular polarizing plate or a display device, the layer formed by fixing the vertically oriented rod-shaped liquid crystal compound is preferably a positive C plate, and the horizontally oriented disc-shaped liquid crystal compound is fixed. The layer is preferably a negative C plate.
- the positive C plate (positive C plate) and the negative C plate (negative C plate) are defined as follows.
- the refractive index in the slow axis direction in the film plane (the direction in which the refractive index in the plane is maximized) is nx
- the refractive index in the direction orthogonal to the slow phase axis in the plane in the plane is ny
- the refraction in the thickness direction is nz
- the positive C plate satisfies the relation of the formula (C1)
- the negative C plate satisfies the relation of the formula (C2).
- the positive C plate shows a negative value for Rth
- the negative C plate shows a positive value for Rth.
- Equation (C1) nz> nx ⁇ ny Equation (C2) nz ⁇ nx ⁇ ny
- ⁇ includes not only the case where both are completely the same but also the case where both are substantially the same.
- substantially the same means, for example, “nx ⁇ ny” when the absolute value of (nx-ny) x d (where d is the thickness of the film) is 0 to 10 nm, preferably 0 to 5 nm. "include.
- the feature of the optical film of the present invention is an optically anisotropic layer (A), an optically anisotropic layer (B), and an optically anisotropic layer (C), which are three layers in which an oriented liquid crystal compound is fixed.
- the optical anisotropic layer (A) and at least one of the optically anisotropic layer (B) are directly laminated with the optically anisotropic layer (C), and the optical anisotropic layer (C) is directly laminated.
- the point that the optical orientation polymer is present on the surface of the layer (C) on the side in contact with the optically anisotropic layer (A) or the optically anisotropic layer (B) can be mentioned.
- the optical film of the present invention has an optically anisotropic layer (A), an optically anisotropic layer (B), and an optically anisotropic layer (C), which are three layers in which an oriented liquid crystal compound is fixed. Then, at least one of the optically anisotropic layer (A) and the optically anisotropic layer (B) is directly laminated with the optically anisotropic layer (C), and the optically anisotropic layer (C) is formed.
- A optically anisotropic layer
- B optically anisotropic layer
- C optically anisotropic layer
- the surface of the optically anisotropic layer (C) on the side in contact with the optically anisotropic layer (A) or the optically anisotropic layer (B) is the optically anisotropic layer (C) and the optically anisotropic layer.
- TOF-SIMS time-of-flight secondary ion mass spectrometry
- the optically anisotropic layer (C) is optically different from the surface of the optically anisotropic layer (C) on the side in contact with the optically anisotropic layer (A) or the optically anisotropic layer (B), that is, the optically anisotropic layer (C). If a photo-oriented polymer having a photo-oriented group is present at the interface with the rectangular layer (A) or the optically anisotropic layer (B), a fragment derived from the photo-oriented group is detected at the same position near the interface. Will be done.
- composition distribution of the optically anisotropic layer (C) and the optically anisotropic layer (A) or the optically anisotropic layer (B) in the thickness direction is determined from the air interface side of any of the optically anisotropic layers. Analysis is performed by repeating irradiation with an ion beam and measurement with TOF-SIMS. In addition, in the irradiation of the ion beam and the measurement by TOF-SIMS, after performing the component analysis of the region from the surface to the thickness direction of 1 to 2 nm (hereinafter, “surface region”), the thickness direction is further 1 to several 100 nm. The series of operations for digging and analyzing the components of the next surface region is repeated.
- the distribution of the optically anisotropic layer in the thickness direction of the optically anisotropic layer (C) and the optically anisotropic layer (A) or the optically anisotropic layer (B) is optically oriented.
- the analysis is performed by measuring the secondary ion intensity from the unit having a group.
- Examples of the type of ion beam include an ion beam using an argon gas cluster ion gun (Ar-GCIB gun).
- FIG. 1 shows a schematic cross-sectional view of the first embodiment of the optical film of the present invention.
- the optical film 10 shown in FIG. 1 has an optically anisotropic layer (A) 1a, an optically anisotropic layer (B) 1b, and an optically anisotropic layer (C) 1c in this order.
- the optically anisotropic layer (C) 1c is preferably a layer formed by fixing a vertically oriented rod-shaped liquid crystal compound or a horizontally oriented disk-shaped liquid crystal compound, and is a layer formed by fixing a vertically oriented rod-shaped liquid crystal compound. It is more preferable to have.
- the optically anisotropic layer (A) 1a is preferably a layer formed by immobilizing a vertically oriented disk-shaped liquid crystal compound, and the optically anisotropic layer (B) 1b is twisted oriented with the thickness direction as the spiral axis. It is preferable that the layer is formed by immobilizing the rod-shaped liquid crystal compound.
- FIG. 2 shows a schematic cross-sectional view of a second embodiment of the optical film of the present invention.
- the optical film 20 shown in FIG. 2 has an optically anisotropic layer (A) 2a, an optically anisotropic layer (C) 2c, and an optically anisotropic layer (B) 2b in this order.
- the optically anisotropic layer (C) 2c is preferably a layer formed by fixing a vertically oriented rod-shaped liquid crystal compound or a horizontally oriented disk-shaped liquid crystal compound, and is a layer formed by fixing a vertically oriented rod-shaped liquid crystal compound. It is more preferable to have.
- the optically anisotropic layer (A) 2a is preferably a layer formed by immobilizing a horizontally oriented rod-shaped liquid crystal compound, and the optically anisotropic layer (B) 2b is twist-oriented with the thickness direction as the spiral axis. It is preferable that the layer is formed by immobilizing a rod-shaped liquid crystal compound.
- optically anisotropic layer (A) The in-plane retardation of the optically anisotropic layer (A) at a wavelength of 550 nm is preferably 140 to 220 nm, and is black when visually recognized from the front direction or an oblique direction of an organic EL display device to which the optical film of the present invention is applied as a circular polarizing plate. 150 to 200 nm is more preferable in terms of the point at which the tinting of black is further suppressed (hereinafter, also simply referred to as “the point at which the tinting of black is further suppressed”).
- the angle ⁇ 1 formed by the longitudinal direction of the optical film and the in-plane slow phase axis of the optically anisotropic layer (A) is preferably 5 to 50 °. 5 to 40 ° is more preferable, and 5 to 25 ° is even more preferable. Further, it is preferably composed of a layer formed by using a composition containing a rod-shaped liquid crystal compound, and most preferably the rod-shaped liquid crystal compound is horizontally oriented.
- the angle ⁇ 1 formed by the longitudinal direction of the optical film and the in-plane slow phase axis of the optically anisotropic layer (A) is preferably 40 to 85 °.
- 50 to 85 ° is more preferable, and 65 to 85 ° is even more preferable. Further, it is preferably composed of a layer formed by using a composition containing a disc-shaped liquid crystal compound, and most preferably the disc-shaped liquid crystal compound is vertically oriented.
- optically anisotropic layer (B) is preferably a layer formed by immobilizing a twist-oriented liquid crystal compound having a spiral axis in the thickness direction. It is preferably a layer in which a chiral nematic phase having a so-called spiral structure is fixed.
- a mixture of a liquid crystal compound showing a nematic liquid crystal phase and a chiral agent described later is preferable to use. The meaning of the "fixed" state is as described above.
- the value of the product ⁇ nd of the refractive index anisotropy ⁇ n of the optically anisotropic layer (B) and the thickness d of the optically anisotropic layer (B) measured at a wavelength of 550 nm is preferably 140 to 220 nm, and the color is black. Is more preferably 150 to 210 nm, and even more preferably 160 to 200 nm in that
- the refractive index anisotropy ⁇ n means the refractive index anisotropy of the optically anisotropy layer.
- the above ⁇ nd is measured by using an AxoScan (polarimeter) device manufactured by Axometrics and using the device analysis software of the same company.
- the twist angle of the liquid crystal compound is preferably 90 ⁇ 30 ° (within the range of 60 to 120 °), and 90 ⁇ 20 ° (in the range of 60 to 120 °) in that the coloring of black color is more suppressed. (Within the range of 70 to 110 °) is more preferable, and 90 ⁇ 10 ° (within the range of 80 to 100 °) is further preferable.
- the twist angle is measured by using an AxoScan (polarimeter) device manufactured by Axometrics and using the device analysis software of the same company.
- the liquid crystal compound when the liquid crystal compound is twisted oriented, the liquid crystal compound from one main surface to the other main surface of the optically anisotropic layer (B) is twisted about the thickness direction of the optically anisotropic layer (B). Intended to be.
- the orientation direction (in-plane slow phase axial direction) of the liquid crystal compound differs depending on the position of the optically anisotropic layer (B) in the thickness direction.
- the in-plane slow phase axis of the optically anisotropic layer (A) and the in-plane slow phase axis on the surface of the optically anisotropic layer (B) on the optically anisotropic layer (A) side may be parallel. preferable.
- the angle between the in-plane slow phase axis on the surface of the optically anisotropic layer (B) on the optically anisotropic layer (A) side and the longitudinal direction of the elongated optical film is ⁇ 1 described above. Corresponds to.
- chiral agent As the chiral agent used for forming the torsional orientation of the liquid crystal compound, various known chiral agents can be used.
- the chiral agent has a function of inducing a helical structure of a liquid crystal compound. Since the chiral compound has a different sense or spiral pitch of the induced spiral depending on the compound, it may be selected according to the purpose.
- a known compound As the chiral agent, a known compound can be used, but it is preferable to have a cinnamoyl group.
- Examples of chiral agents include liquid crystal device handbooks (Chapter 3, 4-3, TN, chiral agents for STN, p.
- JP-A-2003-287623 examples of the compounds described in JP-A-2002-302487, JP-A-2002-80478, JP-A-2002-80851, JP-A-2010-181852, JP-A-2014-034581 and the like are exemplified. To.
- the chiral agent generally contains an asymmetric carbon atom, but an axial asymmetric compound or a surface asymmetric compound containing no asymmetric carbon atom can also be used as the chiral agent.
- Examples of axial or asymmetric compounds include binaphthyl, helicene, paracyclophane and derivatives thereof.
- the chiral agent may have a polymerizable group. When both the chiral agent and the liquid crystal compound have a polymerizable group, the repeating unit derived from the polymerizable liquid crystal compound and the repeating unit derived from the chiral agent are derived by the polymerization reaction between the polymerizable chiral agent and the polymerizable liquid crystal compound.
- the polymerizable group of the polymerizable chiral agent is preferably a group of the same type as the polymerizable group of the polymerizable liquid crystal compound. Therefore, the polymerizable group of the chiral agent is preferably an unsaturated polymerizable group, an epoxy group or an aziridinyl group, more preferably an unsaturated polymerizable group, and more preferably an ethylenically unsaturated polymerizable group. Especially preferable. Further, the chiral agent may be a liquid crystal compound.
- an isosorbide derivative As the chiral agent, an isosorbide derivative, an isomannide derivative, a binaphthyl derivative and the like can be preferably used.
- an isosorbide derivative a commercially available product such as LC-756 manufactured by BASF may be used.
- the content of the chiral agent in the liquid crystal composition is preferably 0.01 to 200 mol%, more preferably 1 to 30 mol% of the amount of the liquid crystal compound.
- optically anisotropic layer (C) is a layer formed by immobilizing a vertically oriented rod-shaped liquid crystal compound or a horizontally oriented disc-shaped liquid crystal compound containing a photo-oriented polymer described later.
- the in-plane retardation of the optically anisotropic layer (C) at a wavelength of 550 nm is preferably 0 to 10 nm.
- the retardation in the thickness direction of the optically anisotropic layer (C) at a wavelength of 550 nm is ⁇ 140 to ⁇ 20 nm. Is preferable.
- the retardation in the thickness direction of the optically anisotropic layer (C) at a wavelength of 550 nm is 20 to 140 nm. Is preferable.
- the in-plane retardation is more preferably 0 to 5 nm in that the tinting of black color is more suppressed.
- the retardation in the thickness direction is more preferably ⁇ 130 to ⁇ 30 nm and more preferably ⁇ 120 to ⁇ 40 nm in that the tinting of black color is more suppressed.
- the optically anisotropic layer (A) when the above-mentioned optically anisotropic layer (A) is a layer made of a vertically oriented disk-shaped liquid crystal compound, the optically anisotropic layer (A), the optically anisotropic layer (B), and the optics are used. It is preferable that the anisotropic layer (C) is laminated in this order.
- the optically anisotropic layer (A) is a layer made of a horizontally oriented rod-shaped liquid crystal compound, the optically anisotropic layer (A), the optically anisotropic layer (C), and the optically anisotropic layer are formed. It is preferable that (B) is laminated in this order.
- the method for producing the above-mentioned optical film is not particularly limited, and a known method can be adopted.
- the above-mentioned method for producing an optical film can be continuously carried out by roll-to-roll.
- an optically anisotropic layer (A) to an optically anisotropic layer (C) are sequentially produced on a long support using a polymerizable liquid crystal composition described later to produce an optical film.
- a polymerizable liquid crystal composition is applied onto a long support to form an optically anisotropic layer (C), and then the polymerizable liquid crystal composition is applied onto the optically anisotropic layer (C).
- an optically anisotropic layer (B) By coating, an optically anisotropic layer (B) is formed, and further, a polymerizable liquid crystal composition is coated on the optically anisotropic layer (B) to form an optically anisotropic layer (A).
- Optical films can be manufactured. Further, the polymerizable liquid crystal composition is applied onto the long support to form the optically anisotropic layer (C), and then the polymerizable liquid crystal composition is applied onto the optically anisotropic layer (C). After forming the optically anisotropic layer (B) to obtain a laminated body, the optically anisotropic layer (A) formed by separately coating a polymerizable liquid crystal composition on a long support is provided.
- An optical film can be manufactured by adhering to the optically anisotropic layer (B) via an adhesive layer (for example, an adhesive layer or an adhesive layer). Further, the polymerizable liquid crystal composition is applied onto the long support to form the optically anisotropic layer (C), and then the polymerizable liquid crystal composition is applied onto the optically anisotropic layer (C). After forming the optically anisotropic layer (A) to obtain a laminated body, the optically anisotropic layer (B) formed by separately coating a polymerizable liquid crystal composition on a long support is formed. An optical film can be manufactured by adhering it to the optically anisotropic layer (C) via an adhesive layer (for example, an adhesive layer or an adhesive layer).
- an adhesive layer for example, an adhesive layer or an adhesive layer
- optically anisotropic layer (A), optically anisotropic layer (B), and optically anisotropic layer (C) are layers in which an oriented liquid crystal compound is fixed, and include a liquid crystal compound having a polymerizable group. It is preferable that the layer is formed by using a composition (hereinafter, also abbreviated as “polymerizable liquid crystal composition”).
- the type of the liquid crystal compound is not particularly limited. Generally, a liquid crystal compound can be classified into a rod-shaped type (rod-shaped liquid crystal compound) and a disk-shaped type (disk-shaped liquid crystal compound) according to its shape.
- the liquid crystal compound can be classified into a small molecule type and a high molecular type.
- a polymer generally refers to a molecule having a degree of polymerization of 100 or more (Polymer Physics / Phase Transition Dynamics, Masao Doi, p. 2, Iwanami Shoten, 1992).
- any liquid crystal compound can be used, but it is preferable to use a rod-shaped liquid crystal compound or a disk-shaped liquid crystal compound (discotic liquid crystal compound), and it is more preferable to use a rod-shaped liquid crystal compound.
- Two or more kinds of rod-shaped liquid crystal compounds, two or more kinds of discotic liquid crystal compounds, or a mixture of a rod-shaped liquid crystal compound and a discotic liquid crystal compound may be used.
- rod-shaped liquid crystal compound for example, those described in claim 1 of JP-A No. 11-513019 and paragraphs 0026 to 0098 of JP-A-2005-289980 can be preferably used.
- discotic liquid crystal compound for example, those described in paragraphs 0020 to 0067 of JP-A-2007-108732 and paragraphs 0013 to 0108 of JP-A-2010-244033 can be preferably used.
- the rod-shaped liquid crystal compound may be a forward wavelength dispersive liquid crystal compound or a reverse wavelength dispersive liquid crystal compound, but when it is a forward wavelength dispersive liquid crystal compound, it is an optical film. It is preferable in that the manufacturing cost is reduced and the durability is improved.
- the forward wavelength dispersible liquid crystal compound means a measured wavelength when the in-plane retardation (Re) value in the visible light range of an optically anisotropic layer produced using this liquid crystal compound is measured. The Re value decreases as the value increases.
- the liquid crystal compound having a reverse wavelength dispersibility means a compound in which the Re value increases as the measured wavelength increases when the Re value is similarly measured.
- the type of the polymerizable group of the liquid crystal compound is not particularly limited, a functional group capable of an addition polymerization reaction is preferable, a polymerizable ethylenically unsaturated group or a ring-polymerizable group is more preferable, and a (meth) acryloyl group or a vinyl group is preferable. , Styryl group, or allyl group is more preferable.
- the optically anisotropic layer produced in the present invention is a layer formed by fixing a liquid crystal compound having a polymerizable group (a rod-shaped liquid crystal compound having a polymerizable group or a discotic liquid crystal compound) by polymerization or the like. Yes, it is no longer necessary to show liquid crystallinity after forming a layer.
- the content of the liquid crystal compound in the polymerizable liquid crystal composition is not particularly limited, but is 60% by mass or more with respect to the total mass (solid content) of the polymerizable liquid crystal composition in that the orientation state of the liquid crystal compound can be easily controlled. Is preferable, and 70% by mass or more is more preferable.
- the upper limit is not particularly limited, but is preferably 99% by mass or less, and more preferably 97% by mass or less.
- the polymerizable liquid crystal composition may contain components other than the liquid crystal compound.
- the polymerizable liquid crystal composition may contain a polymerization initiator.
- the polymerization initiator include known polymerization initiators, photopolymerization initiators and thermal polymerization initiators, and photopolymerization initiators are preferable.
- the content of the polymerization initiator in the polymerizable liquid crystal composition is not particularly limited, but is preferably 0.01 to 20% by mass, preferably 0.5 to 10% by mass, based on the total mass (solid content) of the polymerizable liquid crystal composition. More preferably by mass.
- the polymerizable liquid crystal composition may contain a photosensitizer.
- the type of the photosensitizer is not particularly limited, and examples thereof include known photosensitizers.
- the content of the photosensitizer in the polymerizable liquid crystal composition is not particularly limited, but is preferably 0.01 to 20% by mass, preferably 0.5 to 20% by mass, based on the total mass (solid content) of the polymerizable liquid crystal composition. 10% by mass is more preferable.
- the polymerizable liquid crystal composition may contain a polymerizable monomer different from the liquid crystal compound having a polymerizable group.
- the polymerizable monomer include a radically polymerizable compound and a cationically polymerizable compound, and a polyfunctional radically polymerizable monomer is preferable.
- the polymerizable monomer include the polymerizable monomers described in paragraphs 0018 to 0020 in JP-A-2002-296423.
- the content of the polymerizable monomer in the polymerizable liquid crystal composition is not particularly limited, but is preferably 1 to 50% by mass, more preferably 5 to 30% by mass, based on the total mass of the liquid crystal compound.
- the polymerizable liquid crystal composition may contain a surfactant.
- the surfactant include conventionally known compounds, but fluorine-based compounds are preferable. Specific examples thereof include the compounds described in paragraphs 0028 to 0056 of JP-A-2001-330725 and the compounds described in paragraphs 0069 to 0126 of Japanese Patent Application Laid-Open No. 2003-295212.
- the polymerizable liquid crystal composition may contain a polymer.
- the polymer include cellulose esters.
- examples of the cellulose ester include those described in paragraph 0178 in JP-A-2000-155216.
- the content of the polymer in the polymerizable liquid crystal composition is not particularly limited, but is preferably 0.1 to 10% by mass, more preferably 0.1 to 8% by mass, based on the total mass of the liquid crystal compound.
- the polymerizable liquid crystal composition forming the optically anisotropic layer (C) contains a photoacid generator.
- the photoacid generator include onium salt compounds, trichloromethyl-s-triazines, sulfonium salts, iodonium salts, quaternary ammonium salts, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds.
- an onium salt compound, an imide sulfonate compound, or an oxime sulfonate compound is preferable, and an onium salt compound or an oxime sulfonate compound is more preferable.
- the photoacid generator can be used alone or in combination of two or more.
- the polymerizable liquid crystal composition may contain an additive (orientation control agent) that promotes horizontal orientation or vertical orientation in order to bring the liquid crystal compound into a horizontal or vertical orientation state.
- an additive orientation control agent
- photo-oriented polymer (hereinafter, formally abbreviated as "photo-oriented polymer of the present invention") contained in the optically anisotropic layer (C) of the optical film of the present invention is a polymer having a photo-oriented group. Is.
- the photo-oriented group of the photo-aligned polymer of the present invention has a photo-alignment function in which rearrangement or an heterogeneous chemical reaction is induced by irradiation with light having anisotropy (for example, planar polarization).
- a photo-oriented group having at least one of dimerization and isomerization due to the action of light is preferable because it refers to a group having, has excellent orientation uniformity, and has good thermal stability and chemical stability.
- the group to be quantified by the action of light include the skeleton of at least one derivative selected from the group consisting of a lauric acid derivative, a coumarin derivative, a chalcone derivative, a maleimide derivative, and a benzophenone derivative.
- Preferred examples include a group having a group.
- the group to be isomerized by the action of light specifically, at least one selected from the group consisting of, for example, an azobenzene compound, a stilbene compound, a spiropyran compound, a cinnamic acid compound, and a hydrazono- ⁇ -ketoester compound.
- Preferred examples include groups having a skeleton of a species compound.
- the optically anisotropic layer formed on the upper layer is composed of a cinnamoyl group, an azobenzene group, a carconyl group, and a coumarin group because the liquid crystal orientation of the optically anisotropic layer formed on the upper layer becomes better even with a small exposure amount. It is preferably a group selected from the group.
- the photo-oriented polymer of the present invention is a photo-oriented polymer containing a repeating unit having a photo-oriented group and a repeating unit having a fluorine atom or a silicon atom at the time of forming the optically anisotropic layer (C). Is preferable. Further, the photo-oriented polymer of the present invention is at least one selected from the group consisting of light, heat, acid and base because the liquid crystal orientation of the optically anisotropic layer formed on the upper layer becomes better.
- the repeating unit A has a repeating unit A containing a cleaving group which decomposes to form a polar group by the action of the above, and the repeating unit A has a cleaving group in the side chain, and a fluorine atom or a fluorine atom or a fluorine atom or It is preferably a photo-oriented polymer having a silicon atom (hereinafter, also abbreviated as “cleavable photo-oriented polymer”).
- the "polar group” included in the repeating unit A means a group having at least one hetero atom or a halogen atom, and specifically, for example, a hydroxyl group, a carbonyl group, a carboxy group, an amino group, or a nitro group.
- the "cleaving group that produces a polar group” refers to a group that produces the above-mentioned polar group by cleavage, but in the present invention, it also includes a group that reacts with an oxygen molecule after radical cleavage to generate a polar group.
- cleavage-type photo-oriented polymer examples include the photo-oriented polymers described in paragraphs [0014] to [0049] of International Publication No. 2018/216812, and the contents of these paragraphs are described in this paragraph. Incorporated into the specification.
- photo-orientation polymer containing a repeating unit having a fluorine atom or a silicon atom include a repeating unit having a fluorine atom or a silicon atom represented by the following formula (1) or the formula (2) and photo-orientation.
- a copolymer having a repeating unit having a group (hereinafter, also abbreviated as "specific copolymer") is preferably mentioned.
- the repeating unit having a fluorine atom or a silicon atom represented by the following formula (1) or formula (2) is decomposed by at least one action selected from the group consisting of light, heat, acid and base.
- a repeating unit containing a cleavage group that produces a polar group is decomposed by at least one action selected from the group consisting of light, heat, acid and base.
- r and s each independently represent an integer of 1 or more.
- RB1 and RB2 each independently represent a hydrogen atom or a substituent.
- Y 1 and Y 2 independently represent -O- or -NR Z- , respectively.
- R Z represents a hydrogen atom or a substituent.
- LB1 represents a linking group having an r + 1 valence.
- LB2 represents a s + 1 valent linking group.
- B1 represents a group represented by the following formula (B1). However, when * in the following equation ( B1 ) represents a coupling position with LB1 and r is an integer of 2 or more, the plurality of B1s may be the same or different.
- B2 represents a group represented by the following formula (B2).
- * in the following equation ( B2 ) represents a coupling position with LB2 and s is an integer of 2 or more, the plurality of B2s may be the same or different.
- * represents a bonding position.
- n represents an integer of 1 or more.
- the plurality of n may be the same or different from each other.
- m represents an integer of 2 or more.
- R b1 represents a hydrogen atom or a substituent.
- R b2 , R b3 , and R b4 independently represent a hydrogen atom or a substituent, respectively.
- the two R b3s may be coupled to each other to form a ring
- the plurality of R b2s may be the same or different from each other
- the plurality of R b3s may be the same.
- L b1 represents an n + 1 valent linking group.
- L b2 represents a linking group having an m + 1 valence.
- Z represents an aliphatic hydrocarbon group having a fluorine atom or an organosiloxane group.
- the aliphatic hydrocarbon group may have an oxygen atom, and the plurality of Zs may be the same or different.
- examples of the substituent represented by RB1 include known substituents. Of these, an alkyl group having 1 to 12 carbon atoms is preferable, and a methyl group is more preferable.
- Y 1 independently represents -O- or -NR Z-
- R Z represents a hydrogen atom or a substituent.
- the substituent of R Z include known substituents, and a methyl group is preferable.
- Y 1 it is preferable to represent —O— or —NH—, and more preferably —O—.
- LB1 represents a linking group having an r + 1 valence.
- the r + 1-valent linking group is an r + 1-valent hydrocarbon group having 1 to 24 carbon atoms which may have a substituent, and a part of the carbon atoms constituting the hydrocarbon group is substituted with a heteroatom.
- a hydrocarbon group which may be present is preferable, and an aliphatic hydrocarbon group which may contain an oxygen atom or a nitrogen atom having 1 to 10 carbon atoms is more preferable.
- a 2- to 3-valent linking group is preferable, and a divalent linking group is more preferable.
- r represents an integer of 1 or more.
- an integer of 1 to 3 is preferable, an integer of 1 to 2 is more preferable, and 1 is even more preferable.
- examples of the substituent represented by RB2 include known substituents. Of these, an alkyl group having 1 to 12 carbon atoms is preferable, and a methyl group is more preferable.
- Y 2 represents -O- or -NR Z- .
- R Z represents a hydrogen atom or a substituent. Examples of the substituent of R Z include known substituents, and a methyl group is preferable.
- Y 2 it is preferable to represent —O— or —NH—, and more preferably —O—.
- LB2 represents a s + 1 valent linking group.
- the s + 1-valent linking group is an s + 1-valent hydrocarbon group having 1 to 24 carbon atoms which may have a substituent, and a part of the carbon atoms constituting the hydrocarbon group is substituted with a heteroatom.
- a hydrocarbon group which may be present is preferable, and an aliphatic hydrocarbon group which may contain an oxygen atom or a nitrogen atom having 1 to 10 carbon atoms is more preferable.
- s + 1 valent linking group a divalent linking group is preferable.
- s represents an integer of 1 or more.
- an integer of 1 to 2 is preferable, and 1 is more preferable.
- R b1 As the substituent represented by R b1 , an aliphatic hydrocarbon group having 1 to 18 carbon atoms is preferable, an alkyl group having 1 to 12 carbon atoms is more preferable, and a methyl group is used. Is particularly preferable.
- R b1 is preferably a substituent.
- R b2 in the above formula (B1) examples include known substituents, and examples thereof include the groups exemplified by the substituents of R b1 in the above formula (B1). Further, R b2 preferably represents a hydrogen atom.
- L b1 represents an n + 1-valent linking group
- the n + 1-valent linking group is an n + 1-valent hydrocarbon group having 1 to 24 carbon atoms which may have a substituent.
- a hydrocarbon group in which a part of carbon atoms constituting the hydrocarbon group may be substituted with a heteroatom is preferable, and an aliphatic hydrocarbon group may contain an oxygen atom or a nitrogen atom having 1 to 10 carbon atoms. Is more preferable.
- n + 1-valent linking group a 2- to 4-valent linking group is preferable, a 2- to 3-valent linking group is more preferable, and a divalent linking group is further preferable.
- n represents an integer of 1 or more.
- an integer of 1 to 5 is preferable, an integer of 1 to 3 is more preferable, and 1 is even more preferable.
- Z represents an aliphatic hydrocarbon group having a fluorine atom or an organosiloxane group.
- the aliphatic hydrocarbon group may have an oxygen atom, and the plurality of Zs may be the same or different.
- the aliphatic hydrocarbon group having a fluorine atom include a fluorine atom-containing alkyl group, one or more of -CH 2- constituting the fluorine atom-containing alkyl group substituted with -O-, and a fluorine atom-containing alkenyl. Fluorine and the like can be mentioned.
- the number of carbon atoms of the aliphatic hydrocarbon group having a fluorine atom is not particularly limited, and is preferably 1 to 30, more preferably 3 to 20, and even more preferably 3 to 10.
- the number of fluorine atoms contained in the aliphatic hydrocarbon group having a fluorine atom is not particularly limited, and is preferably 1 to 30, more preferably 5 to 25, still more preferably 7 to 20.
- Examples of the substituent represented by R b3 and R b4 in the above formula (B2) include known substituents, and examples thereof include the groups exemplified by the substituent represented by R b1 in the above formula (B1). Further, in R b3 , it is preferable that the two Rb 3s are bonded to each other to form a ring, and it is more preferable that the two Rb 3s are bonded to each other to form a cyclohexane ring. Further, R b4 preferably represents a hydrogen atom.
- L b2 represents an m + 1 valent linking group.
- the m + 1-valent linking group is an m + 1-valent hydrocarbon group having 1 to 24 carbon atoms which may have a substituent, and a part of the carbon atoms constituting the hydrocarbon group is substituted with a heteroatom.
- a hydrocarbon group which may be present is preferable, and an aliphatic hydrocarbon group which may contain an oxygen atom or a nitrogen atom having 1 to 10 carbon atoms is more preferable.
- m + 1 valent linking group a trivalent to tetravalent linking group is preferable, and a tetravalent linking group is more preferable.
- m represents an integer of 2 or more.
- an integer of 2 to 4 is preferable, and an integer of 2 to 3 is more preferable.
- repeating unit including the group represented by the above formula (B1) include the repeating units represented by the following formulas B-1 to B-22, and the group represented by the above formula (B2) can be used.
- Specific examples of the repeating unit including the repeating unit include the repeating units represented by the following formulas B-23 to B-24.
- the content of the repeating unit having a group represented by the formula (1) or (2) in the photoalignable polymer is not particularly limited, and the liquid crystal orientation of the optically anisotropic layer formed on the upper layer is better. For this reason, 3% by mass or more is preferable, 5% by mass or more is more preferable, 10% by mass or more is further preferable, 20% by mass or more is particularly preferable, and 95% by mass or more is preferable with respect to all the repeating units of the optical orientation polymer. The following is preferable, 80% by mass or less is more preferable, 70% by mass or less is further preferable, 60% by mass or less is particularly preferable, and 50% by mass or less is most preferable.
- the structure of the main chain of the repeating unit having a photo-oriented group is not particularly limited, and known structures can be mentioned.
- a skeleton selected from the group consisting of aromatic esters are preferred.
- a skeleton selected from the group consisting of (meth) acrylic, siloxane, and cycloolefin is more preferable, and (meth) acrylic skeleton is even more preferable.
- repeating units having a photo-oriented group include the following.
- the content of the repeating unit having a photo-oriented group in the photo-aligned polymer is not particularly limited, and the photo-aligned polymer has a better liquid crystal orientation in the optically anisotropic layer formed on the upper layer. It is preferably 5 to 60% by mass, more preferably 10 to 50% by mass, still more preferably 15 to 40% by mass, based on all the repeating units.
- the specific copolymer further has a repeating unit having a crosslinkable group in addition to the repeating unit having a group represented by the above-mentioned formula (1) or (2) and the repeating unit having a photo-oriented group. You may.
- the type of the crosslinkable group is not particularly limited, and examples thereof include known crosslinkable groups. Among them, an epoxy group, an epoxycyclohexyl group, an oxetanyl group, an acryloyl group, a methacryloyl group, a vinyl group, a styryl group, and an allyl group can be mentioned.
- the structure of the main chain of the repeating unit having a crosslinkable group is not particularly limited, and known structures can be mentioned, for example, (meth) acrylic type, styrene type, siloxane type, cycloolefin type, methylpentene type, amide type, and the like.
- a skeleton selected from the group consisting of aromatic ester-based materials is preferable.
- a skeleton selected from the group consisting of (meth) acrylic, siloxane, and cycloolefin is more preferable, and (meth) acrylic skeleton is even more preferable.
- repeating unit having a crosslinkable group examples include the following.
- the content of the repeating unit having a crosslinkable group in the specific copolymer is not particularly limited, and all the repetitions of the photooriented polymer are made because the liquid crystal orientation of the optically anisotropic layer formed on the upper layer becomes better. It is preferably 10 to 60% by mass, more preferably 20 to 50% by mass, based on the unit.
- Examples of the monomer (radical polymerizable monomer) forming other repeating units other than the above include acrylic acid ester compounds, methacrylic acid ester compounds, maleimide compounds, acrylamide compounds, acrylonitrile, maleic acid anhydrides, and styrene compounds. And vinyl compounds can be mentioned.
- the method for synthesizing the photo-orientating polymer of the present invention is not particularly limited, and has, for example, a monomer forming a repeating unit having a group represented by the above-mentioned formula (1) or (2), and the above-mentioned photoreactive group. It can be synthesized by mixing a monomer forming a repeating unit and a monomer forming any other repeating unit and polymerizing in an organic solvent using a radical polymerization initiator.
- the weight average molecular weight (Mw) of the photooriented polymer of the present invention is not particularly limited, but is preferably 25,000 or more because the liquid crystal orientation of the optically anisotropic layer formed on the upper layer becomes better. 25,000 to 500,000 is more preferable, 25,000 to 300,000 is further preferable, and 30,000 to 150,000 is particularly preferable.
- the weight average molecular weight of the photo-oriented polymer and the surfactant described later is a value measured by a gel permeation chromatograph (GPC) method under the conditions shown below.
- the substrate is a plate that supports the optically anisotropic layer.
- a transparent substrate is preferable.
- the transparent substrate is intended to be a substrate having a visible light transmittance of 60% or more, and the transmittance is preferably 80% or more, more preferably 90% or more.
- the retardation value (Rth (550)) in the thickness direction at a wavelength of 550 nm of the substrate is not particularly limited, but is preferably ⁇ 110 to 110 nm, and more preferably ⁇ 80 to 80 nm.
- the in-plane retardation value (Re (550)) at a wavelength of 550 nm of the substrate is not particularly limited, but is preferably 0 to 50 nm, more preferably 0 to 30 nm, still more preferably 0 to 10 nm.
- the material for forming the substrate a polymer having excellent optical performance transparency, mechanical strength, thermal stability, moisture shielding property, isotropic property and the like is preferable.
- the polymer film that can be used as a substrate include cellulose acylate films (for example, cellulose triacetate film (refractive index 1.48), cellulose diacetate film, cellulose acetate butyrate film, cellulose acetate propionate film).
- Polyolefin films such as polyethylene and polypropylene, polyester films such as polyethylene terephthalate and polyethylene naphthalate, polyether sulfone films, polyacrylic films such as polymethylmethacrylate, polyurethane films, polycarbonate films, polysulfone films, polyether films, polymethylpentene films. , Polyether ketone film, (meth) acrylic nitrile film, and polymer film having an alicyclic structure (Norbornen-based resin (Arton: trade name, JSR), amorphous polyolefin (Zeonex: trade name, Nippon Zeon) Company)).
- the material of the polymer film triacetyl cellulose, polyethylene terephthalate, or a polymer having an alicyclic structure is preferable, and triacetyl cellulose is more preferable.
- the substrate may contain various additives (for example, an optical anisotropy adjuster, a wavelength dispersion adjuster, fine particles, a plasticizer, an ultraviolet inhibitor, a deterioration inhibitor, a release agent, etc.).
- additives for example, an optical anisotropy adjuster, a wavelength dispersion adjuster, fine particles, a plasticizer, an ultraviolet inhibitor, a deterioration inhibitor, a release agent, etc.
- the thickness of the substrate is not particularly limited, but is preferably 10 to 200 ⁇ m, more preferably 10 to 100 ⁇ m, and even more preferably 20 to 90 ⁇ m.
- the substrate may be made of a plurality of laminated sheets.
- the substrate may be subjected to surface treatment (eg, glow discharge treatment, corona discharge treatment, ultraviolet (UV) treatment, flame treatment) on the surface of the substrate in order to improve adhesion to a layer provided on the substrate.
- an adhesive layer undercoat layer
- the substrate is solidified with inorganic particles having an average particle size of about 10 to 100 nm.
- a polymer layer mixed by mass ratio of 5 to 40% by mass may be arranged on one side of the substrate.
- the substrate may be a so-called temporary support. That is, after carrying out the production method of the present invention, the substrate may be peeled off from the optically anisotropic layer.
- the surface of the substrate may be directly subjected to the rubbing treatment. That is, a substrate that has been subjected to a rubbing treatment may be used.
- the direction of the rubbing treatment is not particularly limited, and the optimum direction is appropriately selected according to the direction in which the liquid crystal compound is desired to be oriented.
- a processing method widely adopted as a liquid crystal alignment processing step of an LCD (liquid crystal display) can be applied. That is, a method of obtaining orientation by rubbing the surface of the substrate in a certain direction with paper, gauze, felt, rubber, nylon fiber, polyester fiber, or the like can be used.
- the alignment film may be arranged on the substrate.
- the alignment film can be a rubbing treatment of an organic compound (preferably a polymer), an oblique deposition of an inorganic compound, the formation of a layer with microgrooves, or an organic compound (eg, ⁇ -tricosan) by the Langmuir-Blojet method (LB film). It can be formed by means such as accumulation of acid (acid, dioctadecylmethylammonium chloride, methyl stearylate). Further, an alignment film in which an alignment function is generated by applying an electric field, applying a magnetic field, or irradiating with light (preferably polarized light) is also known.
- the procedure for forming the optically anisotropic layer is not particularly limited, and for example, a method of applying a polymerizable liquid crystal composition containing the above-mentioned liquid crystal compound having a polymerizable group onto a substrate and performing a drying treatment as necessary. (Hereinafter, also referred to simply as "coating method"), and a method of separately forming an optically anisotropic layer and transferring it onto a substrate can be mentioned. Above all, the coating method is preferable from the viewpoint of productivity. Hereinafter, the coating method will be described in detail.
- the coating method is not particularly limited, and examples thereof include a wire bar coating method, an extrusion coating method, a direct gravure coating method, a reverse gravure coating method, and a die coating method. If necessary, after the composition is applied, a treatment for drying the coating film applied on the substrate may be carried out. By carrying out the drying treatment, the solvent can be removed from the coating film.
- the film thickness of the coating film is not particularly limited, but is preferably 0.1 to 20 ⁇ m, more preferably 0.2 to 15 ⁇ m, and even more preferably 0.5 to 10 ⁇ m.
- the formed coating film is subjected to an orientation treatment to orient the polymerizable liquid crystal compound in the coating film.
- the alignment treatment can be performed by drying the coating film at room temperature or by heating the coating film.
- the liquid crystal phase formed by the orientation treatment can generally be transferred by a change in temperature or pressure.
- a lyotropic liquid crystal compound it can also be transferred by a composition ratio such as the amount of solvent.
- the conditions for heating the coating film are not particularly limited, but the heating temperature is preferably 50 to 250 ° C, more preferably 50 to 150 ° C, and the heating time is preferably 10 seconds to 10 minutes. Further, after heating the coating film, the coating film may be cooled, if necessary, before the curing treatment (light irradiation treatment) described later.
- the cooling temperature is preferably 20 to 200 ° C, more preferably 30 to 150 ° C.
- the coating film on which the polymerizable liquid crystal compound is oriented is subjected to a curing treatment.
- the method of curing treatment performed on the coating film on which the polymerizable liquid crystal compound is oriented is not particularly limited, and examples thereof include light irradiation treatment and heat treatment. Among them, the light irradiation treatment is preferable, and the ultraviolet irradiation treatment is more preferable from the viewpoint of manufacturing suitability.
- the irradiation conditions of the light irradiation treatment are not particularly limited, but an irradiation amount of 50 to 1000 mJ / cm 2 is preferable.
- the atmosphere during the light irradiation treatment is not particularly limited, but a nitrogen atmosphere is preferable.
- the surface of the optically anisotropic layer (C) on the side in contact with the optically anisotropic layer (A) or the optically anisotropic layer (B) is optically anisotropic.
- photoalignment treatment for example, a method of irradiating a coating film (including a cured film having been cured) of a polymerizable liquid crystal composition with polarized light or irradiating the surface of the coating film with unpolarized light from an oblique direction. Can be mentioned.
- the polarization to be irradiated is not particularly limited, and examples thereof include linear polarization, circular polarization, and elliptically polarization, and linear polarization is preferable.
- the "diagonal direction" for irradiating non-polarized light is not particularly limited as long as it is tilted by a polar angle ⁇ (0 ⁇ ⁇ 90 °) with respect to the normal direction of the coating film surface, depending on the purpose. However, it is preferable that ⁇ is 20 to 80 °.
- the wavelength in polarized light or unpolarized light is not particularly limited as long as it is light to which the photoaligning group is exposed, and examples thereof include ultraviolet rays, near-ultraviolet rays, and visible light, and near-ultraviolet rays having a diameter of 250 to 450 nm are preferable.
- the light source for irradiating polarized or unpolarized light include a xenon lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, and a metal halide lamp.
- an interference filter, a color filter, or the like for ultraviolet rays or visible rays obtained from such a light source the wavelength range to be irradiated can be limited.
- linear polarization can be obtained by using a polarizing filter or a polarizing prism for the light from these light sources.
- the integrated amount of polarized or unpolarized light is not particularly limited, and is preferably 1 to 300 mJ / cm 2 and more preferably 5 to 100 mJ / cm 2 .
- the polarized or unpolarized illuminance is not particularly limited, and is preferably 0.1 to 300 mW / cm 2 , more preferably 1 to 100 mW / cm 2 .
- the photo-oriented polymer contained in the polymerizable liquid crystal composition is the above-mentioned cleavage-type photo-oriented polymer, it is cleaved before the above-mentioned photo-alignment treatment is performed. It is preferable to perform a light irradiation treatment from the viewpoint that cleavage at the group proceeds and the group containing a fluorine atom or a silicon atom is eliminated.
- the light irradiation treatment may be any treatment as long as it is a treatment in which the photoacid generator is exposed to light, and examples thereof include a method of irradiating with ultraviolet rays.
- a lamp that emits ultraviolet rays such as a high-pressure mercury lamp and a metal halide lamp can be used.
- the irradiation amount is preferably 10 mJ / cm 2 to 50 J / cm 2 , more preferably 20 mJ / cm 2 to 5 J / cm 2 , further preferably 30 mJ / cm 2 to 3 J / cm 2 , and even more preferably 50 to 1000 mJ / cm 2 . Is particularly preferable.
- the light irradiation treatment may be performed after the above-mentioned curing treatment is performed, or may be performed at the same time as the above-mentioned curing treatment.
- the circular polarizing plate of the present invention has the above-mentioned optical film of the present invention and a polarizing element, and the polarizing element is arranged adjacent to the optically anisotropic layer (A) of the optical film. It is a board.
- the optically anisotropic layer (A) is arranged closer to the polarizing element than the optically anisotropic layer (B) and the optically anisotropic layer (C). It is a circular polarizing plate.
- the circular polarizing plate 30 of the present invention includes a polarizing element 3 and an optical film 10.
- the splitter 3 is arranged on the side opposite to the optically anisotropic layer 1c side of the optical film 10.
- the circularly polarizing plate 40 of the present invention includes a polarizing element 3 and an optical film 20.
- the splitter 3 is arranged on the side opposite to the optically anisotropic layer 2b side of the optical film 20. It is preferable that the absorption axis of the splitter and the longitudinal direction of the elongated optical film are parallel to each other. That is, the angle formed by the absorption axis of the polarizing element and the longitudinal direction of the long optical film is preferably 0 to 10 °.
- the angle formed by the in-plane slow phase axis of the optically anisotropic layer (A) in the first embodiment is preferably 40 to 85 °, more preferably 50 to 85 °, and 65 to 85 °. Is even more preferable.
- the angle formed by the in-plane slow phase axis of the optically anisotropic layer (A) in the second embodiment is preferably 5 to 50 °, more preferably 5 to 40 °, and 5 to 25 °. Is even more preferable.
- the absorption axis of the modulator is usually likely to be located in the longitudinal direction.
- the two when bonding the two so that the absorption axis of the polarizing element and the longitudinal direction of the long optical film are parallel to each other, the two are continuously bonded by roll-to-roll so that the longitudinal directions of the two are aligned. By combining them, a desired circularly polarizing plate can be produced.
- the splitter may be any member as long as it has a function of converting natural light into specific linear polarization, and examples thereof include an absorption type polarizing element.
- the type of the polarizing element is not particularly limited, and a commonly used polarizing element can be used. Examples thereof include an iodine-based polarizing element, a dye-based polarizing element using a dichroic dye, and a polyene-based polarizing element.
- Iodine-based and dye-based polarizing elements are generally produced by adsorbing iodine or a dichroic dye on polyvinyl alcohol and stretching it.
- a protective film may be arranged on one side or both sides of the polarizing element.
- a liquid crystal compound and a dichroic organic dye for example, for example, without using polyvinyl alcohol as a binder as a substituent.
- a dichroic azo dye used for the light-absorbing anisotropic film described in International Publication No. 2017/195833 may be used, and a coated polarizing element produced by coating may be used. That is, the substituent may be a polarizing element formed by using a composition containing a polymerizable liquid crystal compound.
- This coating type polarizing element is a technique for orienting a dichroic organic dye by utilizing the orientation of a liquid crystal compound.
- the polymerizable liquid crystal compound exhibits smectic properties from the viewpoint of increasing the degree of orientation.
- crystallization of the dye is also preferable from the viewpoint of increasing the degree of orientation.
- International Publication No. 2019/131943 describes a structure of a polymer liquid crystal preferable for increasing the degree of orientation.
- the polarizing element in which the dichroic organic dye is oriented by utilizing the orientation of the liquid crystal without stretching has the following characteristics.
- the thickness can be made very thin, about 0.1 ⁇ m to 5 ⁇ m, cracks are less likely to occur when bent as described in JP-A-2019-194685, and thermal deformation is small.
- Patent No. 6483486 As described in the above, even a polarizing plate having a high transmittance exceeding 50% has many advantages such as excellent durability. Taking advantage of these advantages, it can be used for applications that require high brightness, small size and light weight, fine optical system applications, molding applications for parts having curved surfaces, and applications for flexible parts. Of course, it is also possible to peel off the support and transfer the polarizing element for use.
- the transmittance of the polarizing element is preferably 40% or more, more preferably 44% or more, and further preferably 50% or more.
- the luminous efficiency correction single transmittance of the polarizing element is measured using an automatic polarizing film measuring device: VAP-7070 (manufactured by JASCO Corporation).
- Luminosity factor correction single transmittance can be measured as follows. A sample (5 cm ⁇ 5 cm) in which a polarizing element is attached onto glass via an adhesive is prepared. At this time, the polarizing plate protective film is attached to the polarizing element so as to be on the side opposite to the glass (air interface). Set the glass side of this sample toward the light source and measure.
- the method for manufacturing the circularly polarizing plate is not particularly limited, and a known method can be adopted. For example, a method of adhering an optical film and a polarizing element via an adhesive layer can be mentioned.
- the organic EL display device of the present invention has the above-mentioned optical film (or circular polarizing plate).
- the circular polarizing plate is provided on the organic EL display panel of the organic EL display device. That is, the organic EL display device of the present invention has an organic EL display panel and the above-mentioned circular polarizing plate.
- an organic EL display panel, an optical film, and a polarizing element are provided in this order.
- the organic EL display panel is a member in which a plurality of organic compound thin films including a light emitting layer or a light emitting layer are formed between a pair of electrodes of an anode and a cathode, and is a hole injection layer, a hole transport layer, and an electron injection in addition to the light emitting layer. It may have a layer, an electron transport layer, a protective layer, and the like, and each of these layers may have other functions. Various materials can be used to form each layer.
- the above-mentioned optical film can be used as a polarizing element (polarizing plate) for various articles having a curved surface.
- polarizing element polarizing plate
- it can be used for a rollable display having a curved surface, an in-vehicle display, a lens for sunglasses, a lens for goggles for an image display device, and the like. Since the optical film or circular polarizing plate in the present embodiment can be bonded on a curved surface or integrally molded with a resin, it contributes to the improvement of design.
- Stray light with in-vehicle display optical systems such as head-up displays, optical systems such as AR (augmented reality) glasses and VR (virtual reality) glasses, and optical sensors such as LiDAR (Light Detection and Ranging), face recognition systems, and polarized imaging. It is also preferable to use it for the purpose of deterrence.
- AR augmented reality
- VR virtual reality
- optical sensors such as LiDAR (Light Detection and Ranging), face recognition systems, and polarized imaging. It is also preferable to use it for the purpose of deterrence.
- Example 1 ⁇ Preparation of Cellulose Achillate Film (Substrate)> The following composition was put into a mixing tank, stirred, and further heated at 90 ° C. for 10 minutes. Then, the obtained composition was filtered through a filter paper having an average pore diameter of 34 ⁇ m and a sintered metal filter having an average pore diameter of 10 ⁇ m to prepare a dope.
- the solid content concentration of the dope is 23.5% by mass
- the amount of the plasticizer added is the ratio to the cellulose acylate
- Cellulose acylate dope ⁇ Cellulose acylate (acetyl substitution degree 2.86, viscosity average polymerization degree 310) 100 parts by mass sugar ester compound 1 (represented by the following formula (S4)) 6.0 parts by mass sugar ester compound 2 (represented by the following formula (S5)) 2.0 parts by mass silica particle dispersion (AEROSIL R972, Nippon Aerosil () Made by Co., Ltd.) 0.1 part by mass solvent (methylene chloride / methanol / butanol) ⁇
- the dope prepared above was cast using a drum film forming machine.
- the dope was cast from the die so that it was in contact with the metal support cooled to 0 ° C., and then the resulting web (film) was stripped.
- the drum was made of SUS.
- the web (film) obtained by casting from the drum After peeling the web (film) obtained by casting from the drum, it is dried in the tenter device for 20 minutes using a tenter device that clips and conveys both ends of the web at 30 to 40 ° C. during film transfer. did. Subsequently, the web was rolled and then dried by zone heating. The resulting web was knurled and then rolled up.
- the film thickness of the obtained cellulose acylate film was 40 ⁇ m
- the in-plane retardation Re (550) at a wavelength of 550 nm was 1 nm
- the thickness direction retardation Rth (550) at a wavelength of 550 nm was 26 nm.
- Alkaline saponification treatment After passing the above-mentioned cellulose acylate film through a dielectric heating roll having a temperature of 60 ° C. and raising the film surface temperature to 40 ° C., an alkaline solution having the composition shown below is applied to the band surface of the film using a bar coater.
- the film was applied at a coating amount of 14 ml / m 2 and conveyed under a steam-type far-infrared heater manufactured by Noritake Co., Ltd. Limited, which was heated to 110 ° C. for 10 seconds. Subsequently, 3 ml / m 2 of pure water was subsequently applied using a bar coater.
- the film was transported to a drying zone at 70 ° C. for 10 seconds and dried to prepare a cellulose acylate film treated with alkali saponification.
- the alignment film coating solution having the following composition was continuously applied to the surface of the cellulose acylate film subjected to the alkali saponification treatment with a # 14 wire bar. It was dried with warm air at 60 ° C. for 60 seconds and further with warm air at 100 ° C. for 120 seconds.
- Alignment film coating liquid ⁇ The following polyvinyl alcohol 10 parts by mass water 371 parts by mass methanol 119 parts by mass glutaraldehyde (bridge agent) 0.5 parts by mass citric acid ester (manufactured by Sankyo Chemical Co., Ltd.) 0.175 parts by mass ⁇ ⁇
- composition for forming an optically anisotropic layer (1a) containing a disk-shaped liquid crystal compound having the following composition was applied onto the rubbing-treated alignment film using a Gieser coating machine to form a composition layer. Then, the obtained composition layer was heated with warm air at 80 ° C. for 2 minutes for drying of the solvent and orientation aging of the disc-shaped liquid crystal compound. Subsequently, the obtained composition layer is irradiated with UV (500 mJ / cm 2 ) at 80 ° C. to fix the orientation of the liquid crystal compound, and the optical anisotropic layer corresponding to the optically anisotropic layer (A) is obtained. The sex layer (1a) was formed.
- the thickness of the optically anisotropic layer (1a) was 1.1 ⁇ m.
- the retardation at 550 nm was 168 nm. It was confirmed that the average inclination angle of the disk-shaped liquid crystal compound with respect to the film surface was 90 °, and the disk-shaped liquid crystal compound was oriented perpendicular to the film surface.
- the angle of the slow axis of the optically anisotropic layer (1a) is parallel to the rotation axis of the rubbing roller, and the width direction of the film is 0 ° (the longitudinal direction is 90 ° counterclockwise and ⁇ 90 ° clockwise). ),
- the slow axis was ⁇ 14 ° when viewed from the optically anisotropic layer (1a) side.
- composition for forming an optically anisotropic layer (1a) The following disk-shaped liquid crystal compound 1 80 parts by mass The following disk-shaped liquid crystal compound 2 20 parts by mass The following alignment film surface alignment agent 1 0.55 parts by mass The following fluorine-containing compound A 0.1 part by mass The following fluorine-containing compound B 0.05 parts by mass The following fluorine-containing compound C 0.21 parts by mass Ethylene oxide-modified trimethylolpropantriacrylate (V # 360, manufactured by Osaka Organic Chemical Co., Ltd.) 10 parts by mass Photopolymerization initiator (Irgacure907, manufactured by BASF) 3.0 parts by mass Methyl ethyl ketone 200 parts by mass ⁇
- Fluorine-containing compound A in the following formula, a and b represent the content (mass%) of each repeating unit with respect to all repeating units, a represents 90% by mass, and b represents 10% by mass).
- Fluorine-containing compound B (The numerical value in each repeating unit represents the content (mass%) with respect to all repeating units, the content of the repeating unit on the left side is 32.5% by mass, and the content of the repeating unit on the right side is 67. It was 5% by mass.)
- Fluorine-containing compound C (The numerical value in each repeating unit represents the content (mass%) with respect to all repeating units, the content of the repeating unit on the left side is 25% by mass, and the content of the repeating unit in the middle is 25% by mass. The content of the repeating unit on the right side was 50% by mass.
- a heater (75 ° C.) was installed on the opposite side of the surface so that the distance from the film was 5 mm, and the film was dried for 2 minutes.
- the mixture was heated with warm air at 60 ° C. for 1 minute, and irradiated with ultraviolet rays having an irradiation amount of 100 mJ / cm 2 using a 365 nm UV-LED while purging nitrogen so that the atmosphere had an oxygen concentration of 100 ppm or less.
- the precursor layer was formed by annealing at 120 ° C. for 1 minute with warm air.
- the surface of the obtained precursor layer was irradiated with UV light (ultra-high pressure mercury lamp; UL750; manufactured by HOYA) at room temperature at 7.9 mJ / cm 2 (wavelength: 313 nm).
- a composition layer having an orientation control ability was formed.
- the film thickness of the formed composition layer was 0.5 ⁇ m.
- the in-plane retardation Re at a wavelength of 550 nm was 0 nm, and the thickness direction retardation Rth at a wavelength of 550 nm was ⁇ 68 nm. It was confirmed that the average inclination angle of the rod-shaped liquid crystal compound with respect to the film surface in the long axis direction was 90 °, and the rod-shaped liquid crystal compound was oriented perpendicular to the film surface. In this way, the optically anisotropic layer (1c) corresponding to the optically anisotropic layer (C) was formed.
- composition for forming an optically anisotropic layer (1c) The following rod-shaped liquid crystal compound (A) 100 parts by mass polymerizable monomer (A-400, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) 4.0 parts by mass The following polymerization initiator S-1 (oxym type) 5.0 parts by mass The following Photoacid generator D-1 3.0 parts by mass The following polymer M-1 2.0 parts by mass The following vertical alignment agent S01 2.0 parts by mass The following photo-orientation polymer A-1 2.0 parts by mass The following Surface active agent B-1 0.2 parts by mass Methyl ethyl ketone 42.3 parts by mass Methyl isobutyl ketone 627.5 parts by mass ⁇ ⁇
- Rod-shaped liquid crystal compound (A) (hereinafter, a mixture of compounds)
- Photo-Orientation Polymer A-1 (The numerical values described in each repeating unit represent the content (mass%) of each repeating unit with respect to all the repeating units, and 43% by mass, 27% by mass, 30 from the left repeating unit. The weight average molecular weight was 69,800.)
- Surfactant B-1 weight average molecular weight was 2200
- optically anisotropic layer (1b) (Formation of optically anisotropic layer (1b)) Next, the composition for forming an optically anisotropic layer (1b) containing a rod-shaped liquid crystal compound having the following composition is coated on the optically anisotropic layer (1c) prepared above by using a Gieser coating machine, and 80 It was heated with warm air at ° C for 60 seconds. Subsequently, the obtained composition layer is irradiated with UV (500 mJ / cm 2 ) at 80 ° C. to fix the orientation of the liquid crystal compound, and the optical anisotropic layer corresponding to the optically anisotropic layer (B) is obtained. The sex layer (1b) was formed.
- the thickness of the optically anisotropic layer (1b) was 1.2 ⁇ m, ⁇ nd at a wavelength of 550 nm was 164 nm, and the twist angle of the liquid crystal compound was 81 °. Assuming that the width direction of the film is 0 ° (the longitudinal direction is 90 °), the orientation axis angle of the liquid crystal compound when viewed from the optically anisotropic layer (1b) side is 14 ° on the air side and the optically anisotropic layer (1b). The side in contact with 1c) was 95 °.
- the orientation axis angle of the liquid crystal compound contained in the optically anisotropic layer is 0 ° with respect to the width direction of the substrate, and the substrate is observed from the surface side of the optically anisotropic layer in a clockwise direction (clockwise). Time is shown as negative, and counterclockwise (counterclockwise) is shown as positive.
- the twist angle of the liquid crystal compound is such that the substrate is observed from the surface side of the optically anisotropic layer, and the liquid crystal compound on the substrate side (back side) is based on the orientation axis direction of the liquid crystal compound on the surface side (front side).
- the orientation axis direction of is clockwise (clockwise), it is expressed as negative, and when it is counterclockwise (counterclockwise), it is expressed as positive.
- composition for forming an optically anisotropic layer (1b) 100 parts by mass of the above rod-shaped liquid crystal compound (A) ethylene oxide-modified trimethyl propantriacrylate (V # 360, manufactured by Osaka Organic Chemical Co., Ltd.) 4 parts by mass of a photopolymerization initiator (Irgacure819, manufactured by BASF) 3 parts by mass below Left-handed torsion chiral agent (L1) 0.60 parts by mass
- the above-mentioned fluorine-containing compound C 0.08 parts by mass Methyl ethyl ketone 156 parts by mass ⁇ ⁇
- an optically anisotropic layer (1c), an optically anisotropic layer (1b), and an optically anisotropic layer (1a) are laminated in this order on a long cellulose acylate film. (1c-1b-1a) was obtained.
- ⁇ Manufacturing of linear polarizing plate 1> The surface of the support of the cellulose triacetate film TJ25 (manufactured by FUJIFILM Corporation: thickness 25 ⁇ m) was subjected to alkali saponification treatment. Specifically, after immersing the support in a 1.5N sodium hydroxide aqueous solution at 55 ° C. for 2 minutes, the support is washed in a water washing bath at room temperature, and further, 0.1N sulfuric acid at 30 ° C. is added. Neutralized using. After neutralization, the support was washed in a water washing bath at room temperature and further dried with warm air at 100 ° C. to obtain a polarizing element protective film.
- a roll-shaped polyvinyl alcohol (PVA) film having a thickness of 60 ⁇ m was continuously stretched in an aqueous iodine solution in the longitudinal direction and dried to obtain a polarizing element having a thickness of 13 ⁇ m.
- the luminous efficiency correction single transmittance of the polarizing element was 43%.
- the absorption axis direction and the longitudinal direction of the stator were the same.
- the above-mentioned polarizing element protective film was bonded to one surface of the above-mentioned polarizing element using the following PVA adhesive to prepare a linear polarizing plate 1.
- PVA adhesive 100 parts by mass of a polyvinyl alcohol-based resin having an acetoacetyl group (average degree of polymerization: 1200, degree of saponification: 98.5 mol%, degree of acetoacetylation: 5 mol%) and 20 parts by mass of methylol melamine at 30 ° C.
- a PVA adhesive was prepared as an aqueous solution which was dissolved in pure water and adjusted to a solid content concentration of 3.7% by mass under the above temperature conditions.
- the polarizing element protective film, the polarizing element, the optically anisotropic layer (1a), the optically anisotropic layer (1b), and the optically anisotropic layer (1c) are laminated in this order, and the absorber is absorbed.
- the angle formed by the axis and the slow axis of the optically anisotropic layer (1a) was ⁇ 76 °.
- the orientation axis angle of the liquid crystal compound on the optically anisotropic layer (1a) side of the optically anisotropic layer (1b) is 14 ° with the width direction as a reference, and the optically anisotropic layer (1a). It was consistent with the slow axis direction of.
- Example 2 ⁇ Formation of alignment film>
- the photoalignment film forming material described in Example 1 of WO2016 / 002722 was applied onto the elongated cellulose acylate film prepared above. Then, the coating film was heated to 125 ° C. with warm air to form a hard film. Then, it was irradiated with polarized ultraviolet rays of 313 nm.
- optically anisotropic layer (B) An optically anisotropic layer coating liquid (1b) containing the rod-shaped liquid crystal compound having the above composition was applied onto the prepared photoalignment film using a Gieser coating machine, and heated with warm air at 80 ° C. for 60 seconds. Subsequently, the obtained composition layer is irradiated with UV (500 mJ / cm 2 ) at 80 ° C. to fix the orientation of the liquid crystal compound, and the optical anisotropic layer corresponding to the optically anisotropic layer (B) is obtained. The sex layer (2b) was formed.
- the thickness of the optically anisotropic layer (2b) was 1.2 ⁇ m, ⁇ nd at a wavelength of 550 nm was 164 nm, and the twist angle of the liquid crystal compound was 81 °. Assuming that the width direction of the film is 0 ° (the longitudinal direction is 90 °), the orientation axis angle of the liquid crystal compound when viewed from the optically anisotropic layer (2b) side is -76 ° on the air side, which is a cellulose acylate film. The contact side was 5 °.
- the orientation axis angle of the liquid crystal compound contained in the optically anisotropic layer is 0 ° with respect to the width direction of the substrate, and the substrate is observed from the surface side of the optically anisotropic layer in a clockwise direction (clockwise). Time is shown as negative, and counterclockwise (counterclockwise) is shown as positive.
- the twist angle of the liquid crystal compound is such that the substrate is observed from the surface side of the optically anisotropic layer, and the liquid crystal compound on the substrate side (back side) is based on the orientation axis direction of the liquid crystal compound on the surface side (front side).
- the orientation axis direction of is clockwise (clockwise), it is expressed as negative, and when it is counterclockwise (counterclockwise), it is expressed as positive.
- the average inclination angle of the rod-shaped liquid crystal compound with respect to the film surface in the long axis direction was 90 °, and the rod-shaped liquid crystal compound was oriented perpendicular to the film surface.
- the optically anisotropic layer (2c) corresponding to the optically anisotropic layer (C) was formed.
- optically anisotropic layer (2a) (Formation of optically anisotropic layer (2a)) Next, the optically anisotropic layer coating liquid (2a) containing the rod-shaped liquid crystal compound having the following composition is coated on the optically anisotropic layer (2c) prepared above by using a Gieser coating machine, and the temperature is 80 ° C. It was heated with warm air for 60 seconds. Subsequently, the obtained composition layer is irradiated with UV (500 mJ / cm 2 ) at 80 ° C. to fix the orientation of the liquid crystal compound, and the optical anisotropic layer corresponding to the optically anisotropic layer (A) is obtained. The sex layer (2a) was formed. The thickness of the optically anisotropic layer (2a) was 1.2 ⁇ m.
- the retardation at 550 nm was 168 nm. It was confirmed that the average inclination angle of the rod-shaped liquid crystal compound with respect to the film surface in the long axis direction was 0 °, and the rod-shaped liquid crystal compound was oriented horizontally with respect to the film surface. Further, assuming that the width direction of the film is 0 ° (the longitudinal direction is 90 °), the slow phase axis is ⁇ 76 ° when viewed from the optically anisotropic layer (2a) side.
- composition for forming an optically anisotropic layer (2a) ⁇ 100 parts by mass of the above rod-shaped liquid crystal compound (A) ethylene oxide-modified trimethylolpropane triacrylate (V # 360, manufactured by Osaka Organic Chemical Co., Ltd.) 4 parts by mass of a photopolymerization initiator (Irgacure819, manufactured by BASF) 3 parts by mass.
- Fluoro-containing compound C 0.08 parts by mass Methyl ethyl ketone 156 parts by mass ⁇
- the cellulose acylate film on the optically anisotropic layer (2c) side was peeled off to expose the surface of the optically anisotropic layer (2c) in contact with the cellulose acylate film.
- the surface of the exposed optically anisotropic layer (2c) and the surface side of the optically anisotropic layer (2b) formed on the elongated cellulose acylate film produced above are subjected to an ultraviolet curable adhesive. And pasted on a continuous machine.
- the cellulose acylate film on the optically anisotropic layer (2b) side was peeled off to expose the surface of the optically anisotropic layer (2b) in contact with the cellulose acylate film.
- a circular polarizing plate (P2) composed of an optical film (2b-2c-2a) and a linear polarizing plate was produced.
- the polarizing element protective film, the polarizing element, the optically anisotropic layer (2a), the optically anisotropic layer (2c), and the optically anisotropic layer (2b) are laminated in this order, and the absorber is absorbed.
- the angle between the axis and the slow axis of the optically anisotropic layer (2a) was 14 °.
- orientation axis angle of the liquid crystal compound on the optically anisotropic layer (2c) side of the optically anisotropic layer (2b) is 76 ° with the width direction as a reference, and the optically anisotropic layer (2a). It was consistent with the slow axis direction of.
- Example 3 The composition for forming an optically anisotropic layer (1a) of Example 1 is changed to the following composition for forming an optically anisotropic layer (3a), and the composition for forming an optically anisotropic layer (1c) is described below.
- the composition for forming an optically anisotropic layer (3c) was changed to the composition for forming an optically anisotropic layer (3c), and the composition for forming an optically anisotropic layer (1b) was changed to the following composition for forming an optically anisotropic layer (3b).
- a circular polarizing plate (P3) composed of an optical film (3c-3b-3a) and a linear polarizing plate was produced by the same method as in Example 1.
- the thickness of the optically anisotropic layer (3a) is 1.3 ⁇ m
- the thickness of the optically anisotropic layer (3c) is 0.7 ⁇ m
- the thickness of the optically anisotropic layer (3b) is 1.5 ⁇ m. Met.
- the twist angle was the same as that of the optically anisotropic layers (1a), (1c) and (1b) of Example 1.
- composition for forming an optically anisotropic layer (3a) The disk-shaped liquid crystal compound 1 80 parts by mass The disk-shaped liquid crystal compound 2 20 parts by mass The alignment film interface alignment agent 1 1.2 parts by mass The fluorine-containing compound A 0.1 part by mass The following fluorine-containing compound E 0.06 parts by mass The following fluorine-containing compound F 0.21 parts by mass Ethylene oxide-modified trimethylol propantriacrylate (V # 360, manufactured by Osaka Organic Chemical Co., Ltd.) 5 parts by mass The following photopolymerization initiator 1 5.0 Parts by mass Methyl ethyl ketone 200 parts by mass ⁇
- Fluorine-containing compound E (the numerical value in each repeating unit represents the content (mass%) with respect to all repeating units, the content of the repeating unit on the left side is 36% by mass, and the content of the repeating unit on the right side is 64% by mass. there were.)
- Fluorine-containing compound F (the numerical value in each repeating unit represents the content (mass%) with respect to all repeating units, the content of the repeating unit on the left side is 56% by mass, and the content of the repeating unit on the right side is 44% by mass. there were.)
- composition for forming an optically anisotropic layer (3c) 100 parts by mass of the above rod-shaped liquid crystal compound (A) polymerizable monomer (A-400, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) 4.2 parts by mass of the above polymerization initiator S-1 (oxym type) 5.1 parts by mass of the above Photoacid generator D-1 3.0 parts by mass
- the above polymer M-1 2.0 parts by mass
- the above vertical alignment agent S01 1.9 parts by mass
- the following photo-orientation polymer A-2 0.8 parts by mass Diisopropyl Ethylamine 0.2 parts by mass Ethyl propionate 93.8 parts by mass Methyl isobutyl ketone 375.0 parts by mass ⁇ ⁇
- Photo-Orientation Polymer A-2 (The numerical values shown in each repeating unit represent the content (% by mass) of each repeating unit with respect to all the repeating units, and 37% by mass, 27% by mass, 36 from the repeating unit on the left side. It was mass%, and the weight average molecular weight was 74000.)
- Fluorine-containing compound G (The numerical value in each repeating unit represents the content (mass%) with respect to all the repeating units, the content of the repeating unit on the left side is 76% by mass, and the content of the repeating unit on the right side is 24% by mass. The weight average molecular weight was 27300.)
- the optically anisotropic layer (hb) is optically anisotropic.
- the orientation axis angle of the liquid crystal compound was ⁇ 94 ° on the air side and ⁇ 13 ° on the side in contact with the cellulose acylate film.
- the opposite side of the protective film) was continuously bonded using an ultraviolet curable adhesive. In this way, a circular polarizing plate (PH) was produced.
- Ammonia was exposed for 60 minutes by placing an optical film with a glass plate on a screw cap bottle containing a 2 mol% / L methanol solution of ammonia. At this time, the exposed surface was arranged so as to be an optically anisotropic layer (1c) or an optically anisotropic layer (2b). In-plane retardations Re (450), Re (550) and Re (650) at wavelengths of 450 nm, 550 nm and 650 nm were measured using Axoscan from Axometrics.
- Example 4 An optically anisotropic layer (1c), an optically anisotropic layer (1b), and an optically anisotropic layer (1a) were laminated in this order on a long cellulose acylate film in the same manner as in Example 1. An optical film (1c-1b-1a) was obtained. Next, as the linear polarizing plate 2, a polarizing plate SHC-215U manufactured by Polatechno Co., Ltd., in which a polyvinyl alcohol film was dyed with a dichroic organic dye, was prepared. The luminous efficiency correction single transmittance of the polarizing element was 44%.
- the surface of the optically anisotropic layer (1a) of the long optical film (1c-1b-1a) and the corona-treated surface of one side of the long linear polarizing plate 2 are bonded by ultraviolet curable. It was continuously bonded using an agent. Subsequently, the cellulose acylate film of the optically anisotropic layer (1c) was peeled off to expose the surface of the optically anisotropic layer (1c) in contact with the cellulose acylate film. In this way, a circular polarizing plate (P4) was produced.
- Example 5 An optically anisotropic layer (1c), an optically anisotropic layer (1b), and an optically anisotropic layer (1a) were laminated in this order on a long cellulose acylate film in the same manner as in Example 1. An optical film (1c-1b-1a) was obtained.
- a splitter using a dichroic organic dye and a polymerizable liquid crystal was prepared by the following procedure.
- the coating liquid PA1 for forming an alignment layer which will be described later, was continuously coated on a cellulose triacetate film TJ40 (manufactured by Fujifilm: thickness 40 ⁇ m) with a wire bar.
- the support on which the coating film was formed was dried with warm air at 140 ° C.
- PA1 was formed to obtain a TAC film with a photoalignment layer PA1.
- the film thickness of the photoalignment layer PA1 was 0.3 ⁇ m.
- Coating liquid PA1 for forming an oriented layer The following polymer PA-1 100.00 parts by mass The following acid generator PAG-1 5.00 parts by mass The following acid generator CPI-110TF 0.005 parts by mass Xylene 1220.00 parts by mass Methyl isobutyl ketone 122.00 parts by mass- ⁇
- the following composition for forming a light absorption anisotropic layer P2 was continuously applied on the obtained light alignment layer PA1 with a wire bar to form a coating film P2.
- the coating film P2 was heated at 140 ° C. for 30 seconds, and then the coating film P2 was cooled to room temperature (23 ° C.).
- the obtained coating film P2 was heated at 90 ° C. for 60 seconds and cooled again to room temperature.
- a light absorption anisotropic layer P2 was produced on the light alignment layer PA1 by irradiating with an LED (light emitting diode) lamp (center wavelength 365 nm) for 2 seconds under an illuminance of 200 mW / cm 2 .
- the molar content of the radically polymerizable group is 1.17 mmol / g.
- the film thickness of the light absorption anisotropic layer P2 was 1.0 ⁇ m.
- the following cured layer forming composition K1 was continuously applied on the obtained light absorption anisotropic layer P2 with a wire bar to form a coating film.
- the coating film was dried at room temperature, and then irradiated for 15 seconds under an irradiation condition of an illuminance of 28 mW / cm 2 using a high-pressure mercury lamp to prepare a cured layer K1 on the light absorption anisotropic layer P2.
- the film thickness of the cured layer K1 was 0.05 ⁇ m.
- the following oxygen blocking layer forming composition B2 was continuously applied onto the cured layer K1 with a wire bar. Then, by drying with warm air at 100 ° C. for 2 minutes, an oxygen blocking layer B2 having a thickness of 1.0 ⁇ m was formed on the cured layer K1 to prepare a polarizing film 5B containing a light absorption anisotropic layer P2. The luminous efficiency correction single transmittance of the polarizing film 5B was 44%.
- Oxygen blocking layer forming composition B2 ⁇ ⁇
- the oxygen blocking layer B2 side of the polarizing film 5B and the polarizing plate protective film were attached using an adhesive sheet. After that, only the TJ40 of the polarizing film 4B is peeled off, and the peeled surface, the surface of the optically anisotropic layer (1a) of the long optical film (1c-1b-1a), and the ultraviolet curable adhesive are used. They were stuck together continuously. Subsequently, the cellulose acylate film of the optically anisotropic layer (1c) was peeled off to expose the surface of the optically anisotropic layer (1c) in contact with the cellulose acylate film. In this way, a circular polarizing plate (P5) was produced.
- Example 6 A circular polarizing plate (P6) was produced in the same direction as in Example 4, except that the film thickness of the light absorption anisotropic layer P2 in Example 4 was 0.8 ⁇ m. The luminous efficiency correction single transmittance of the polarizing element was 45%.
- the exposed surface was arranged so as to be an optically anisotropic layer (1c).
- an optically anisotropic layer (1c) To determine the difference in effective reflectance before and after wet and heat durability, create a reflective substrate by attaching aluminum foil to a 100 ⁇ thick PET film using an adhesive sheet, and use a spectrocolorimeter (manufactured by Konica Minolta) to create the following. Evaluated according to the criteria. AA: Reflectance difference is 0.2% or less A: Reflectance difference is larger than 0.2% and 0.5% or less B: Reflectance difference is larger than 0.5% and 2 .0% or less C: Reflectance difference is greater than 2.0%
- the circularly polarizing plates of Examples 4 to 6 when used as an antireflection film of an organic EL display device, they can show the same initial performance as that of Example 1 and can reduce the change in display performance before and after the endurance of wet heat. confirmed. Further, it was confirmed that the circularly polarizing plates of Examples 4 and 6 were able to confirm an increase in transmittance when displayed in white, and could achieve power saving of the organic EL element.
- Circularly polarizing plate 1a 2a Optically anisotropic layer (A) 1b, 2b Optically anisotropic layer (B) 1c, 2c Optically anisotropic layer (C) 3 Polarizer
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Abstract
Priority Applications (4)
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CN202180052023.5A CN115989451A (zh) | 2020-08-25 | 2021-08-25 | 光学膜、圆偏振片、有机电致发光显示装置 |
JP2022545668A JP7506754B2 (ja) | 2020-08-25 | 2021-08-25 | 光学フィルム、円偏光板、有機エレクトロルミネッセンス表示装置 |
KR1020237005696A KR20230038789A (ko) | 2020-08-25 | 2021-08-25 | 광학 필름, 원편광판, 유기 일렉트로 루미네선스 표시 장치 |
US18/169,687 US20230194763A1 (en) | 2020-08-25 | 2023-02-15 | Optical film, circularly polarizing plate, and organic electroluminescent display device |
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JP2020157672 | 2020-09-18 | ||
JP2021-009400 | 2021-01-25 | ||
JP2021009400 | 2021-01-25 |
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US18/169,687 Continuation US20230194763A1 (en) | 2020-08-25 | 2023-02-15 | Optical film, circularly polarizing plate, and organic electroluminescent display device |
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PCT/JP2021/031144 WO2022045187A1 (fr) | 2020-08-25 | 2021-08-25 | Film optique, plaque de polarisation circulaire et dispositif d'affichage électroluminescent organique |
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JP (1) | JP7506754B2 (fr) |
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2004240012A (ja) * | 2003-02-04 | 2004-08-26 | Fuji Photo Film Co Ltd | 位相差板および楕円偏光板 |
JP2004258623A (ja) * | 2003-02-03 | 2004-09-16 | Dainippon Printing Co Ltd | 液晶層からなる光学素子及びそれを用いた液晶表示装置 |
WO2006090617A1 (fr) * | 2005-02-25 | 2006-08-31 | Nitto Denko Corporation | Element polarisant, ecran a cristaux liquides, television a cristaux liquides et dispositif d'affichage a cristaux liquides |
JP2017067964A (ja) * | 2015-09-29 | 2017-04-06 | 富士フイルム株式会社 | 光学シートとその製造方法、液晶表示装置 |
WO2018216812A1 (fr) * | 2017-05-26 | 2018-11-29 | 富士フイルム株式会社 | Polymère de photo-alignement, composition de liant, couche de liant, stratifié optique, procédé de production de stratifié optique, et dispositif d'affichage d'image |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
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US9128322B2 (en) | 2013-03-25 | 2015-09-08 | Fujifilm Corporation | Phase difference plate for circularly polarizing plate, circularly polarizing plate, and organic electroluminescence display apparatus |
-
2021
- 2021-08-25 JP JP2022545668A patent/JP7506754B2/ja active Active
- 2021-08-25 WO PCT/JP2021/031144 patent/WO2022045187A1/fr active Application Filing
- 2021-08-25 KR KR1020237005696A patent/KR20230038789A/ko unknown
- 2021-08-25 CN CN202180052023.5A patent/CN115989451A/zh active Pending
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2023
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Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2004258623A (ja) * | 2003-02-03 | 2004-09-16 | Dainippon Printing Co Ltd | 液晶層からなる光学素子及びそれを用いた液晶表示装置 |
JP2004240012A (ja) * | 2003-02-04 | 2004-08-26 | Fuji Photo Film Co Ltd | 位相差板および楕円偏光板 |
WO2006090617A1 (fr) * | 2005-02-25 | 2006-08-31 | Nitto Denko Corporation | Element polarisant, ecran a cristaux liquides, television a cristaux liquides et dispositif d'affichage a cristaux liquides |
JP2017067964A (ja) * | 2015-09-29 | 2017-04-06 | 富士フイルム株式会社 | 光学シートとその製造方法、液晶表示装置 |
WO2018216812A1 (fr) * | 2017-05-26 | 2018-11-29 | 富士フイルム株式会社 | Polymère de photo-alignement, composition de liant, couche de liant, stratifié optique, procédé de production de stratifié optique, et dispositif d'affichage d'image |
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JP7506754B2 (ja) | 2024-06-26 |
CN115989451A (zh) | 2023-04-18 |
US20230194763A1 (en) | 2023-06-22 |
KR20230038789A (ko) | 2023-03-21 |
JPWO2022045187A1 (fr) | 2022-03-03 |
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